Dyeing red with 2,6-dicyano-2&#39;-sulfonamido-4&#39;-amino-azo-benzenes

ABSTRACT

Azo compounds of the formula ##STR1## wherein R 1  is alkyl, alkenyl, aralkyl, aryl or hetaryl, 
     R 2  is hydrogen or alkyl, 
     R 3  is hydrogen, alkyl, halogen, OR 1  etc. 
     R 4  is hydrogen, alkyl, aralkyl, aryl or cycloalkyl, 
     R 5  is hydrogen, alkyl, alkenyl or aralkyl, 
     Y is cyano, halogen, trifluoromethyl, nitro or SO 2  R 1 , 
     Y 1  is halogen or preferably cyano, 
     X 1  is hydrogen or a substituent with a Hammet σ para value of -0.3 to +0.3, 
     X 2  is hydrogen, halogen etc., 
     are useful for dyeing polyester fibre materials in clear red to violet shades with good general fastness properties.

This is a division of application Ser. No. 112,995, filed Jan. 17, 1980,now abandoned; which is a continuation of Ser. No. 110,731, filed Jan.9, 1980, now abandoned; which is a continuation of Ser. No. 884,954,filed Mar. 9, 1978, now abandoned.

The invention relates to azo compounds of the formula ##STR2## whereinR₁ is alkyl, alkenyl, aralkyl, aryl or hetaryl,

R₂ is hydrogen or alkyl,

R₃ is hydrogen, alkyl, halogen, cyano, OR₁ or COOR₁,

R₄ is hydrogen, alkyl, aralkyl, aryl or cycloalkyl, R₅ is hydrogen,alkyl, alkenyl or aralkyl,

Y is cyano, halogen, trifluoromethyl, nitro or SO₂ R₁,

Y₁ is halogen or cyano,

X₁ is hydrogen or a substituent with a Hammet σ para value of -0.3 to+0.3,

X₂ is hydrogen, halogen, OR₁, COOR₁, COOH, NR₂ CHO, CF₃, NR₂ COR₁,N(COR₁)₂, ##STR3## NR₂ SO₂ R₁ or NR₂ SO₂ N(R₂)₂ X₃ is alkyl or X₂ and

X₁ with X₂ or X₃ is the grouping --OCH₂ OCH₂ -- and

R₃ and R₄, as well as R₄ and R₅, can be linked by an alkylene chain, theabovementioned alkyl, aralkyl, alkenyl, aryl and heteryl radicals beingoptionally substituted by non-ionic substituents or COOH.

Suitable substituents X₁ with a Hammet σ para value of -0.3 to +0.3 arethose such as are listed in H. A. Staab "Einfuhrung in die theoretischeorganische Chemie" ("Introduction to Theoretical Organic Chemistry"),Verlag Chemie, Weinheim/Bergstrasse 1970, or are the weaklyelectron-donating or weakly electron-attracting, preferably non-ionicsubstituents customary in dyestuff chemistry, and hydrogen. Exampleswhich may be mentioned are: alkyl, aryl, aralkyl, O-alkyl, O-aryl,O-aralkyl, halogen, --NR₂ COR₁, --N(COR₁)₂, --NR₂ CHO, ##STR4## and--NR₂ SO₂ R₁.

The alkylene chains which can link R₃ and R₄ or R₄ and R₅ preferablycontain 3 to 5 C atoms.

Preferred compounds are those of the formula I, wherein

X₁ denotes hydrogen, alkyl, --O-alkyl, alkyl-(OCH₂ CH₂)_(m) O-- (inwhich m=1-4), aralkyl, aryl, halogen, --O-aryl, --NR₂ CHO, --NR₂ COR₁ orNR₂ SO₂ R₁,

X₂ denotes hydrogen, --O-alkyl, CF₃ or NHCO-alkyl,

X₃ denotes alkyl or X₂ or

X₁ with X₂ or X₃ denotes the grouping --OCH₂ OCH₂ --,

Y denotes cyano, chlorine, bromine, iodine or --SO₂ --alkyl,

Y₁ denotes chlorine, bromine, iodine or cyano,

R₁ denotes alkyl, alkenyl, aralkyl, aryl or hetaryl,

R₂ denotes hydrogen,

R₃ denotes hydrogen, alkyl, O-alkyl or chlorine,

R₄ denotes hydrogen, aralkyl, alkyl or cycloalkyl and

R₅ denotes alkenyl or R₄,

wherein the alkyl radicals mentioned in any desired connection abovepreferably contain 1-4 C atoms and can preferably be monosubstituted byhalogen, --CN, --OH, ##STR5## or aryl, or a group (--OCH₂ CH₂)_(n) OR₁(n=1-8), the alkenyl radicals preferably contain 3-5 C atoms and can beoptionally substituted by halogen, the aralkyl radicals are preferablybenzyl and phenylethyl radicals, which can preferably be monosubstitutedto trisubstituted by alkyl, O-alkyl, halogen and nitro, the arylradicals are preferably phenyl radicals, which can preferably bemonosubstituted to trisubstituted by alkyl, O-alkyl, halogen, --CN, NO₂or --COO-(C₁ -C₄ -alkyl), the hetaryl radicals are preferably pyridine,quinoline or thiophene radicals, and halogen is preferably to beunderstood as bromine or chlorine.

Preferred alkyl radicals are methyl, ethyl, n-propyl and n-butyl. Apreferred aryl radicals is phenyl, and "bulky" radicals (for examplet-butyl) are preferably in those positions where they cause no sterichindrance (for example in the m-position or, preferably, p-position of aphenyl radical).

Cycloalkyl is preferably cyclohexyl.

Preferred compounds in the scope of the compounds of the formula (I) areespecially those which are water-insoluble and in which

X₁ represents hydrogen, alkyl or O-alkyl,

X₂ represents hydrogen,

X₃ represents hydrogen, alkyl or --O-alkyl,

R₁ represents alkyl, aryl or aralkyl,

R₂ represents hydrogen,

R₃ represents hydrogen, alkyl or --O-alkyl,

R₄ represents hydrogen, alkyl or aralkyl,

R₅ represents alkyl or aralkyl,

Y₁ represents chlorine, bromine, iodine or cyano and

Y represents --SO₂ -alkyl or, preferably, chlorine or bromine or iodineor, in particular, cyano, "alkyl", "aralkyl" and "aryl" having theabovementioned meaning.

Those compounds of the formula (I) wherein

X₂, R₂ and R₃ denote hydrogen,

X₃ denotes C₁ -C₄ -alkyl or, preferably, hydrogen,

X₁ denotes C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or CH₃ (OCH₂ CH₂)_(m) O--,

Y and Y₁ denote cyano,

R₁ denotes C₁ -C₄ -alkyl,

R₄ denotes hydrogen or C₁ -C₄ -alkyl, which can be substituted by C₁ -C₄-alkoxy and

R₅ denotes benzyl, phenethyl or C₁ -C₄ -alkyl, which can be substitutedby C₁ -C₄ -alkoxy, are particularly preferred.

The new azo compounds of the formula (I) are prepared in a manner whichis in itself known, for example by coupling diazotised anilines of theformula (II) ##STR6## to coupling components of the formula (III)##STR7## wherein

X₁ -X₃, Y, Y₁ and R₁ -R₅ have the meaning described above.

Those compounds of the formula I wherein Y₁ =CN are preferably preparedby a process in which diazotised anilines of the formula (IV) ##STR8##wherein X₁ -X₃ and Y have the meaning described above and

Y₂ denotes chlorine, bromine or iodine,

are combined with coupling components of the formula (III) to give thecorresponding o-halogenoazo dyestuffs (V) ##STR9## and the halogensubstituent or substituents Y₂ and/or Y in these compounds are replacedby a cyano, nitro or SO₂ --R substituent. Y₂ preferably representsbromine.

These replacement reactions are also known and are described, forexample, in the following Patent literature: DT-OS (German PublishedSpecification) No. 1,544,563=British Patent Specification No. 1,125,638,DT-OS (German Published Specification) Nos. 2,341,109 and 2,456,495,DT-OS (German Published Specification) No. 1,809,921=British PatentSpecification No. 1,255,367, and British Patent Specification No.1,226,950.

The halogen/cyano exchange is preferably carried out by means ofcopper-I cyanide, zinc cyanide or mixtures of these cyanides.

Examples of suitable diazo components of the formula (II) or (IV) are:2,6-dichloroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline,2,6-dibromo-4-methyl-aniline, 2,6-dibromo-3,4-dimethyl-aniline,2,6-dibromo-4-dodecylaniline, 2,6-dibromo-4-cyclohexylaniline,2,6-dibromo-4-ethylaniline, 2,6-dichloro-4-methoxy-aniline,2,6-dibromo-3-methoxy-4-methyl-aniline,2,6-dibromo-3-acetamino-4-methyl-aniline,2,6-dibromo-4-(β-hydroxy-acetyl)-amino-aniline,2,6-dibromo-4-tert.-butyl-aniline, 2-nitro-4-methyl-6-bromo-aniline,2-nitro-4-methoxy-6-bromo-aniline, 2-cyano-4,6-dibromo-aniline,4-dodecylaminocarbonyloxy-2,6-dibromo-aniline and4-phenylaminocarbonyloxy-2,6-dibromo-aniline.

Examples of suitable coupling components of the formula (III) are:3-diethylamino-methanesulphonanilide,3-dipropylamino-methanesulphonanilide,3-dibutylamino-methylsulphonanilide,3-diethylamino-benzenesulphonanilide,3-diethylamino-p-toluenesulphonanilide,3-dibutylamino-p-toluenesulphonanilide,3-dioctylamino-methanesulphonanilide,3-dipropylamino-ω-chlorobutanesulphonanilide,3-diallylamino-methanesulphonanilide,3-di-(β-propoxyethyl)-amino-methanesulphonanilide,3-di(β-butoxyethyl)-amino-benzenesulphonanilide,3-di(β-ethoxyethyl)-amino-toluenesulphonanilide,2-(ethyl-β-cyanoethyl)-amino-4-methanesulphonamido-anisole,3-ethyl-benzyl-amino-methylsulphonanilide,3-phenylamino-methylsulphonanilide, 3-diethylamino-benzylsulphonanilideand 3-diethylamino-dodecylsulphonanilide.

The compounds according to the invention, in particular those in whichY₁ =CN, are valuable dyestuffs which can be used for dyeing synthetictextile materials, in particular textile materials consisting ofsecondary cellulose acetate and cellulose triacetate, polyamide, suchas, for example, polyhexamethyleneadipamide, and especially an aromaticpolyester, such as, for example, polyethylene terephthalate, by dyeingmethods customary for these types of fibres, aqueous or nonaqueousliquors being employed.

In addition, the new dyestuffs can also be used for spin dyeing and meltdyeing polyamides, polyesters, polyurethanes and polyolefins.Furthermore, the dyestuffs are suitable for dyeing hydrocarbons, suchas, for example, heating oil.

Finally, the dyestuffs can be applied to synthetic textile materials bytransfer printing.

The resulting red to violet dyeings have good general fastnessproperties and good depth of colour and are distinguished by aparticularly clear contour shade, such as has hitherto only beenobtained from anthraquinone dyestuffs, but at the cost of a low depth ofcolour.

A particularly good affinity can be achieved here by mixing thedyestuffs of the formula (I). The mixtures can be prepared not only fromthe finished dyestuffs, but also by coupling a diazo component to amixture of the coupling components or by subjecting the o-halogenoazodyestuffs of the formula (V) together, as a mixture, to a nucleophilicreplacement reaction with cyanide, nitrite or sulphinates.

EXAMPLE 1

Preparation of the dyestuffs of the formula ##STR10##

A solution of 26.5 g of 2,6-dibromo-4-methyl-aniline in 125 ml of 60%strength sulphuric acid is diazotised with 17 ml of a 42% strengthnitrosylsulphuric acid at 38°-40° C. The mixture is subsequently stirredfor 60 minutes at 40° C., and the solution of the diazo component isthen added, at 0°-5° C., to a solution or suspension of 24.2 g of3-diethylamino-methanesulphonanilide and 2 g of amidosulphonic acid in200 ml of water. The pH value is increased to 3 by adding sodiumacetate. The precipitate is filtered off and washed several times withwater.

Yield: 45.5 g

10.36 g of the3-methanesulphonamido-4-(2',6'-dibromo-4'-methyl-phenylazo)-N,N-diethylanilinethus obtained are dissolved or suspended in 50 ml of dimethylformamide,together with 2.35 g of zinc cyanide and 0.2 g of copper cyanide, andthe mixture is warmed to 100° C. for 30 minutes. The product isprecipitated with 50 ml of water and 7.5 g of the dicyanoazo dyestuffare filtered off. It dyes polyester fibres in a bluish-tinged red shadewith good fastness properties, in particular fastness to light,sublimation and wet processing.

EXAMPLE 2

Preparation of the dyestuff of the formula ##STR11##

12 ml of 42% strength nitrosylsulphuric acid are added dropwise to asuspension of 20 g of 2,4-dibromo-6-cyanoaniline in 90 ml of 60%strength sulphuric acid at 38°-40° C. in the course of 30 minutes. Themixture is stirred for a further 1 hour at 38°-40° C., and the resultingdiazonium salt solution is then added, at 0°-5° C., to a solution of21.2 g of 3-methanesulphonamido-N,N-diethylaniline hydrochloride in 100ml of water and 20 ml of 10% strength amidosulphonic acid solution. ThepH value is increased to 4 by adding sodium acetate. The product isfiltered off, washed several times with water and dried.

Yield: 35.8 g. The dyestuff dyes polyester in a bluish-tinged red shadewith good fastness properties.

The dyestuffs indicated in the Table which follows are obtained by ananalogous or similar procedure.

    __________________________________________________________________________    Example                             Colour shade                              No.  Formula                        on polyester                              __________________________________________________________________________          ##STR12##                     bluish-tinged red                         4                                                                                   ##STR13##                     "                                         5                                                                                   ##STR14##                     "                                         6                                                                                   ##STR15##                     "                                         7                                                                                   ##STR16##                     "                                         8                                                                                   ##STR17##                     red                                       9                                                                                   ##STR18##                     "                                         10                                                                                  ##STR19##                     "                                         11                                                                                  ##STR20##                     bluish-tinged red                         12                                                                                  ##STR21##                     "                                         13                                                                                  ##STR22##                     "                                         14                                                                                  ##STR23##                     "                                         15                                                                                  ##STR24##                     red                                       16                                                                                  ##STR25##                     "                                         17                                                                                  ##STR26##                     "                                         18                                                                                  ##STR27##                     "                                         19                                                                                  ##STR28##                     bluish-tinged red                         20                                                                                  ##STR29##                     "                                         21                                                                                  ##STR30##                     "                                         22                                                                                  ##STR31##                     "                                         23                                                                                  ##STR32##                     "                                         24                                                                                  ##STR33##                     "                                         25                                                                                  ##STR34##                     ruby                                      26                                                                                  ##STR35##                     "                                         27                                                                                  ##STR36##                     "                                         28                                                                                  ##STR37##                     red-violet                                29                                                                                  ##STR38##                     bluish-tinged red                         30                                                                                  ##STR39##                     "                                         31                                                                                  ##STR40##                     "                                         32                                                                                  ##STR41##                     "                                         33                                                                                  ##STR42##                     "                                         34                                                                                  ##STR43##                     ruby                                      35                                                                                  ##STR44##                     bluish-tinged red                         36                                                                                  ##STR45##                     "                                         37                                                                                  ##STR46##                     red                                       38                                                                                  ##STR47##                     "                                         39                                                                                  ##STR48##                     bluish-tinged red                         40                                                                                  ##STR49##                     "                                         41                                                                                  ##STR50##                     "                                         42                                                                                  ##STR51##                     red                                       43                                                                                  ##STR52##                     "                                         44                                                                                  ##STR53##                     bluish-tinged red                         45                                                                                  ##STR54##                     "                                         46                                                                                  ##STR55##                     ruby                                      47                                                                                  ##STR56##                     bluish-tinged red                         48                                                                                  ##STR57##                     "                                         49                                                                                  ##STR58##                     "                                         50                                                                                  ##STR59##                     "                                         51                                                                                  ##STR60##                     red                                       52                                                                                  ##STR61##                     "                                         53                                                                                  ##STR62##                     "                                         54                                                                                  ##STR63##                     "                                         55                                                                                  ##STR64##                     "                                         56                                                                                  ##STR65##                     bluish-tinged red                         57                                                                                  ##STR66##                     "                                         58                                                                                  ##STR67##                     "                                         59                                                                                  ##STR68##                     "                                         60                                                                                  ##STR69##                     "                                         __________________________________________________________________________     *These and the following longerchain alkyl radicals in the dyestuff           molecules are straightchain radicals                                     

EXAMPLE 61

Preparation of the dyestuff of the formula ##STR70##

A solution of 26.5 g of 2,6-dibromo-4-methyl-aniline in 125 ml of 60%strength sulphuric acid is diazotised with 17 ml of a 42% strengthnitrosylsulphuric acid at 38°-40° C. The mixture is subsequently stirredfor 60 minutes at 40°, and the solution of the diazo component is thenadded, at 0°-5° C., to a solution or suspension of 24.2 g of3-diethylamino-methanesulphonanilide and 2 g of amidosulphonic acid in200 ml of water. The pH value is increased to 3 by adding sodiumacetate. The product is filtered off, and washed several times withwater.

Yield: 45.5 g

The dyestuff dyes polyester fibres in an orange shade with good generalfastness properties, in particular fastness to light, sublimation andwet processing.

The dyestuffs indicated in the Table which follows are obtained by ananalogous or similar procedure.

    ______________________________________                                                                        Colour                                        Exam-                           shades on                                     ple No.                                                                             Formula                   polyester                                     ______________________________________                                        62                                                                                  ##STR71##                  orange                                       63                                                                                  ##STR72##                  orange                                       64                                                                                  ##STR73##                  orange                                       65                                                                                  ##STR74##                  orange                                       66                                                                                  ##STR75##                  orange                                       67                                                                                  ##STR76##                  bluish- tinged red                           ______________________________________                                    

I claim:
 1. In the coloring of fibrous materials red by dyeing orprinting with a dispersion of a dyestuff, the improvement wherein saiddyestuff comprises a red-dyeing azo compound of the formula ##STR77## inwhich X is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, CH₃ (OCH₂ CH₂)_(m) O,chlorine, bromine or hydrogen,m is 1-4, R₁ is C₁ -C₄ -alkyl, benzyl,phenyl or tolyl, R₂ is hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkylsubstituted by C₁ -C₄ -alkoxy, C₂ H₄ OCONHC₄ H₉, C₂ H₄ OCOCH₃ or C₂ H₄OC₂ H₄ OCH₃, and R₃ is benzyl, phenethyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkylsubstituted by C₁ -C₄ -alkoxy, C₂ H₄ OCOHNC₄ H₉, C₂ H₄ OCOCH₃ or C₂ H₄OC₂ H₄ OCH₃.
 2. The process according to claim 1, whereinX is hydrogen,chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, R₁ is C₁ -C₄ -alkyl orphenyl.
 3. The process according to claim 2, in whichR₁ is methyl. 4.The process according to claim 2, wherein said dyestuff is of theformula ##STR78##
 5. Fibrous material dyed or printed red by the processof claim 1.